Azo dyestuffs insoluble in water and fiber dyed therewith



Patented Dec. 10, 1940 AZO DYE STUFFS INSOLUBLE WATER AND FIBER DYED THEREWITH Kurt Schimmelschmidt and Oskar Schneider, Frankfort-on-the-Main, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application July 1, 1939, Serial No. 282,524. In Germany July 5, 1938 Claims.

The present invention relates to azo-dyestu'ffs insoluble in water and to fiber dyed therewith; more particularly it relates to the dyestufis of the following general formula:

a ryl whereinYi stands for hydrogen, a methyl or methoxy group, Y2 stands for hydrogen or a methyl group, always one of the two substituents Y1 and Y2 being hydrogen, X means an alkyl or alkoxy group or a chlorine atom and wherein the phenyl radical a may contain further substituents, advantageously an alkoxy group or a halogen atom.

We have found that valuable azo-dyestufis insoluble in water may be obtained by coupling in substance, on the fiber or on a substratum adapted for the production of lakes any diazocompound with a 3-hydroxydiphenylene-oxide-2- carboxylic acid anilide of the general formula:

wherein Y1 stands for hydrogen, a methyl or methoxy Y2 stands for hydrogen or a methyl group, al-

ways one of the two substituents Y1 and Y2 being hydrogen,

X means an alkyl or alkoxy group or a chlorine atom and wherein the phenyl radical a may contain further substituents, advantage ously an alkoxy group or a halogen atom,

only such dyestuff components being used as do not contain any group imparting solubility in water, such as the sulphonic acid or carboxylic acid group.

When produced on the fiber the azo-dyestufis obtainable by the present invention yield brown, khaki and olive dyeings of very good properties of fastness, particularly of very good fastness to light. In-comparison with comparable azo-dyestuffs described in German Specification No. 594,326 the new dyestuffs surprisingly show a considerable displacement of the colour shade. Furthermore, the dyeings obtainable by the invention only slightly change their shade when boiled with soap and are distinguished by an improved fastness to rubbing. These effects obtained by the introduction of a methyl or methoxy group into 7-position or of a methyl group into o x YiQQC O-NH a Y: III OH N 6-position of the 3-hydroxydiphenylene-oxide-2- carboxylic acid:- arylides could in no way be foreseen.

' 'By' the new process especially khaki shades can be produced of a fastness hitherto unattained with ice colours; it, therefore, represents a valuable advance in the art. e 7

The- 7-methyl-3-hydroxydiphenylene-oxide-2- carboxylic acid anilides used asparent material may be obtained by transforming according to known methods the ,'1-methyl-3-hydroxydiphenylene-oxide obtainable as described in U. S. application Serial No. 120,826, filed January 15, 1937, into the 7-methyl-3-hydroxydiphenylene-oxide- 2-carboxylic acid melting at 293 C.-294 C. and condensing the latter in known manner with the corresponding amines of the benzene series. In a similar manner there may be prepared the "7- methoxyor 6-methyl-3-hydroxydiphenylene oxide-Z-carboxylic acid anilides from the 7- methoxy or 6-methy1-B-hydroxydijohenyleneoxide described in the before-mentioned U. S. application Serial No. 120,826, by way of the '7- methoxy-3- hydroxydiphenylene oxide-Z-carboxylic acid melting at 286 C. or the 6-methyl-3-hydroxydiphenylene-oXide-2-carboxylic acid melting at 282 C.-283 C. t 3 The following examples serve to illustrate the invention, but they are not intended'to limit it thereto, the parts being by weight; the parts by weight and the parts by volume are related to each other as are kilograms to liters: r

1) 1 part of1-(7-methyl-3-hydroxydiphenylene-oxide-2Gearbonylamino) -2-methyl- 4 -meth oxybenzene, melting at 254 C.-255 C. is dissolved in 4 parts by volume of alcohol, 0.47 part by volume of caustic soda solution of 34 B. and 6 parts by volume of water, and the whole is made up to 1000 parts by volume by means of water to which 18.3 parts by volume of caustic soda solu tion of 34 B. and the usual protective colloids have been added. 50 parts of cotton yarn are treated for hour in this grounding solution, squeezed and developed for hour in a diazosolution prepared in the usual manner from 2 parts of 1-amino-2-methyl-4-chlorobenzene and made up to 1000. parts by volume. The yarn is then rinsed, soaped and dried. A khaki shade of very good fastness to wet-processing, to rubbing and to light is obtained.

(2) 36 parts of 1-(7'-methyl-3'-hydroxydiphenylene-oxide-Z'-carbonylamino) -2-methyl-4- methoxybenzene are dissolved in water-with addition of caustic soda solution. After addition of sodium acetate a diazo-solution prepared from 14.1 parts of 1-amino-2-methyl-4-chlorobenzene is added. The yellow-brown dyestuif obtained is filtered with suction,v washed and dried. When produced in the usual manner on a substratum, suitably in the form'of a paste, it yields a yellowbrown lake of good properties. The dyestufi corresponds with the following formula:

CH3 I 0&0 o O-NH-OO on;

I]? on N '(3) 1 part of 1-(7'-methyl-3ehydroxydiphenylene oxide 2' carbonylamino) 2-chl0ro- 4- methoxybenzene, melting at 1262 C.-263 C. .is

dissolved in 4 parts by volume of alcohol, 0.4 part by volume of caustic potash solution of 50 B. and 6 parts by volume of water, and the whole is made up to 1000 parts by volume by means of water to which 18 parts by volume of caustic soda solution of 34 B. and the usual protective colloids have been added. 50 parts of cotton yarn are treated for A; hour in this grounding solution, squeezed and developed for /2 hour in a diazo-solution prepared in the usual manner from 2 parts of 1-amino-2-methy1-3- chlorobenzene and made up to 1000 parts by volume. The yarn is then rinsed, soaped and dried. A greenish khaki shade of very good fastness to wet-processing, to rubbing and to light is obtained.

The idliowingiable indicates a number of other azo-dyestufis obtainable by the invention and having similar properties:

Diem-component Coupling-component Shade 1 l-amino-2-methoxy-5-nitrobenzene t 1- (7' -Inethyl-3-hydroxy-diphenyleneoxide-2-carbonylamino)-2- Olive dark brown.

- methylA-methoxybenzene. 2 1-amino-2-methoxy-5-chlorobenzene Dark brown. .3 l-amino-2-methy1-3-ohlorobenzene Greenish brown. 4 1-amino-2-methyl-5-chlorobenzene D0. 5 2-amino-4A-di-chloro-diphenylether Brown. 6 '1-amino-3-chloro1benzene Olive brown. 7 l-amino-2-chloro-5-trifluoromethyl-benzene do Khaki. 8 1-amino-2-methyl-4-chlorobenzene l- (7 '-methyl-3 hydroxy-diphenyleneoxide-2-carbonylamino) -2.5- Yellowish brown.

dlmethoxybenzene, melting point 230-231 C. 9 l-amino-2-n1ethoxy-5-chlorobenzenen .do Greenish brown. 10 l-amin0-2-nitrobenzene i -do Olive. 1i l-amino-4-nitrobenzene -do Do. 12 1-amin0-2.fi-dichloi'obenzene 1-(7-methyl-3hydroxy-diphenyleneoxide-2'-carbonylammo) -2- Khaki.

methoxy-benzene, melting point 247249 C. 13 1- amino-2-methyl5-nitrobenzene .do .Do. 14 l-amino-2-chlorobenzene 1-(7'-methyl-3-hydroxy-diphenyleneoxide-2-carbonylamino) -2 Olive brown.

methylbenzene, melting point 268-269 C. 15 l-amino-2.4-dimethyl-fi-benzoylaminobenzene. do Khaki. l6 l-amino2-methyl-3-chlorobenzene do Greenish khaki. 17 l-amino-S-chlorobenzene l- (7' -methyl 3 -hydroxydiphenyleneoxide 2 carbonylamino) 2 D0.

ch1oro-4-methoxybenzene. 18 l-ammo-S.5-bistrifluoromethylbenzene do Olive brown. 19 l-amino-2 methyl-4-chlorobenzene o Khaki. 20 1-amino-2-methoxy-5-chlorobenzene 'l-(7 -,methyl -3 -hydroxydiphenyleneoxide-2 oarbonylamino) -2- Dark brown.

,chloro-5-methoxybenzene, melting point 233235 0. 21 l-am no-2-methy1-3-chlorobenzene do Khaki. 22 l-ammo-lmethoxy-5-ehlorobenzene -1-((i' nethyl-3'-l1ydroxydiphenyleneoxide-2'-carbonylamino)-2i5-di- 'Dark brown.

methoxybenzene, melting point 160-161 C. 23 1-amino-2.5-dichlorobenzene do Covered brown. 24 1-2;)mino-2chloro+benzoylamino-fi-methoxy- I do Copper brown.

enzene 25 l-amino-2-methyl-3-chlorobenzene do Brown. 26 l-amino-2-methyl-4-chlorobenzene do Covered brown. 27 l-amino-2-methyl-4-chlorobenzene l-(6-methyl -3 -hydroxydiphenyleneoxide-2'-carbonylami.no) -2- Brown.

- methyl-@methoxybenzene, melting point 226228 G. 28 1-amino-2-methoxy-5-chlorobenzene do' Dark brown. 20 1-8.minO-2.5-dlchl0rnben mm do Greenish brown. 30 l-amino-2-chlorobenzene (lo Olivebrown. 31 l-amino-Z-chloro-4-benzoylamino*5methoxy-, -.do Brown.

' benzene. 32 1-amino-2-methyl-5-chlorobenzene do Do. 33 l-amino-2-methyl-3-ehlorobenzene do Do. 34 l-ammo-2.5-dichlorobenzene l-(6-methyl-3'-hydroxy-diphenyleneoxide-2-carbonylamino) -2- Covered brown.

methoxybenzene, melting point 198l99 C. 35 l-amino-2 methyl-4-ehlorobenzene do l Do. 36 l-amino-Z-methoxy-S-chlorobenzene Dark brown. 37 l-aijmino2-chloro-4-benzoylamino 5-m1ethoxy- Copper brown.

61128118. 38 1-amino-2.5-dichlorobenzene 1-(6-methyl-3'-hydroxy-diphenyleneoxide-2-carbonylamino) 2.5-. Brown. dimethoxyi-chlotobenzene, melting point 234-236" C. 39- 1-am1no-2-methoxy-5-chlorobenzene do Dark brown. 40 l-amino-2-methyl-3-chlorobenzene. do Brown. 41 l-a1nino2methyl-4-chlorobenzene I-(fV-methy Yellowish brown.

chloro-4-methoxy benzene, melt 42 l-am1no-2-methoxy-5-chlorobenzene do Red-brown. 43 l-amino-2.fi-dichlorobenzene Yellowlsh brown. 44 1-amino-2-methyl-4-chlorobenzen 3-hydroxy-diphenyleneoxide-2 carbonyl amino) Do.

methoxy-benzene, melting point 2l5217 G. 45 '1-amino-2-methoxy-dchlorobenzena Red-brown. 46 ,l-amino-3-ch1orobenzene i -Ye1lowish khaki. 47 l-amino-2-methyl-4-chlorobenze et yl-3 -hydroxy-diphenyleneoxide- 2carbonylamino) -2 Khak methoxy-echlorobenzene, melting point 234-235" C. 48 Lamina-2.5-dichlorobenzene Do 49 l-amino-2-chlorobenzene Yellowish khaki. 50 '1-amino2-metl1yl-5-ch1orob K a l. 51 leamino-2-methyl-3-chlorobenzene D0. 52 l-amino-2-chloro-5-trifluoromethylben Do. 53 l-emino-2-methyl-5-nitrobenzene Do. 54 l-amino-2-methyl-5-chlorobenzene -hydroxy diphenyleneoxide -2- curb onylamino)- Brown.

' 2.5-dimethoxybenzene, melting point 234236 O. 55 l-amino-2-metlioxye5-chlorobenzene i; do Dark bro 56 1-amino-2-methyl-3-chlorobenzene Brown. 57 l-amino-2-methyl-5-nitrobenzene do I 0 58 l-amino-2 methyl-4-chlorobenzene 7 -rnethoxy-3 -hydroxy-diphenyleneoxide -'2'-carbonylam1no) D0- 2 methyl-4 methoxy-benzene, melting point 250251 C. 59 l-amino-2-metl1oxy-5chlorobenzene dn Dark brown- 60 l-amino-2;5dichl0r0benvene do Brown. 61 1-an1ino-41nitro rln Diazo-component Coupling-component Shade 62 l-amino-2-methyl-3-chlorobenzene 1- (7'-methoxy-3'- hydroxy-diphenyleneoxide-2-carbonylamino) Brown.

Z-methyl-4-methoxy-benzene, melting point 250-? 0. 63 lermine-2-chloro-4-benzoylamino-5-methoxy- Copper brown.

enzene.

64 l-amino-2-methyl-5-nitrobenzene ;do Brown.

66 1-amino-2-metlioxy-5-nitrobenzene. do: Do.

67 l-amino-2-methyl-4-chlorobenzene -n ethoxy-3-hydroxydiphenyleneoxide-2-carbonylam1no)-2.5- Do.

- dimethoxy-i-chlorobenzene, melting point 273-274" C.

68 l-amino-2-methoxy-fi-chlorobenzene. do Dark brown.

71 1-amino-2.5-dichlorobenzene 1-(7-methoxy 3-hydroxy-diphenyleneoxide- 2' carbonylamino) -2- Do.

methylbenzene, melting point 267 C.

72 l-amino-2-methoxy-5-chlorobenzene 7 Red brown.

73 l-amino-2.5-dich1orobenzene; 1-(7-metl1oxy-3 -hydroxydiphenyleneoxide-2 -carbo nylammo) -2- Brown.

. methoxybenzene, melting point 232233 C.

74 1-amino-2-methyl-3-chlorob n n Do.

75 l-amino-2-methyl-4-chlorobenzene do Do.

76 l-amino-2-methoxy-5-chlorobenzene .d0 Dark brown.

77 l-agnino-z-chloro-4-benzoylamino-5-methoxydn Copper brown.

enzene 78 l-amino-2-methyl-4-chlorobenzene 1-(7"metl1oxy-3-hydroxydiphenyleneoxide-2'-carbony1amino) -2- Brown.

methoxy--chlorobenzene, melting point 273 C.

79 l-amino-2-methoxy-5-chlorobenzene do Dark brown.

81 1-amino2-methyl-Zi-chlorobenzen 0- Do.

82 l-amino-Z-methyl-kchlorobenzen 1-(7-methoxy-3- hydroxydiphenyleneoxide-2' oarbonylamino) -2- Do.

chloro-i-methoxybenzene, melting point 252-253 O.

83 1-amino-2-methoxy-5-chlorobenzene do Violehsh brown.

84 l-amino-Z-methyl-3-chlorobenzene -d0 Brown.

wherein X stands for a member of the group consisting of methyl, methoxy and chlorine, Z1 for a member of the group consisting of hydrogen and methoxy, Z2 for a member of the group consisting of hydrogen and chlorine, and R. stands for a radica1 of the benzene series, yielding, when produced on the fiber, brown, khaki and olive dyeings of very good properties of fastness, particularly of very good fastness to light.

3. The water-insoluble azo-dyestuff of the following formula:

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic and the carboxylic acid group.

We claim:

1. The water-insoluble azo-dyestuifs corresponding with the following general formula:

0 X on oo-NH- ocn i 3 II Y, 1 1 on z, N v

N CH:

wherein Y1 stands for one of the group consisting of hydrogen, methyl and methoxy, Y2 for one of the group consisting of hydrogen and methyl, always one of the two substituents Y1 and Y2 being hydrogen, X stands for a member of the group consisting of methyl, methoxy and chlorine, Z1 for a member of the group consisting of hydrogen and methoxy, Z2 for a member of the group consisting of hydrogen and chlorine, and R stands for a radical of the benzene series, yielding, when produced on the fiber, brown, khaki and olive dyeings of very good properties of fastness, particularly of very good fastness to light.

2. The water-insoluble azo-dyestufis corresponding with the following general formula:

OH II N O0 cm NO 0 x Z: CHWCO-NH I N OH Zi L yielding, when produced on the fiber, olive dark- I brown dyeings of very good fastness to wetprocessing, to rubbing and to light.

5. The water-insoluble azo-dyestuif of the following formula:

5 yielding, when produced on the 'fiber, greencoma-O0 CH:

ish-khaki dyeings of very good fastness to wetprocessing, to rubbing and to light.

6. Fiber dyed with the dyestufis as claimed in claim 1.

7. Fiber dyed with the dyestuffs as claimed 5 in claim 2.

8. Fiber dyed with the dyestufi as claimed in claim 3.

9. Fiber dyed with the dyestuff as claimed in claim 4.

10. Fiber dyed with the dyestuff as claimed in claim 5.

KURT SCI-HMMELSCHMIDT. OSKAR SCHNEIDER. 

